WO2013128928A1 - 表面被覆アルミニウム含有亜鉛系めっき鋼板及びその製造方法 - Google Patents

表面被覆アルミニウム含有亜鉛系めっき鋼板及びその製造方法 Download PDF

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Publication number
WO2013128928A1
WO2013128928A1 PCT/JP2013/001203 JP2013001203W WO2013128928A1 WO 2013128928 A1 WO2013128928 A1 WO 2013128928A1 JP 2013001203 W JP2013001203 W JP 2013001203W WO 2013128928 A1 WO2013128928 A1 WO 2013128928A1
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WIPO (PCT)
Prior art keywords
mass
steel sheet
plated steel
range
water
Prior art date
Application number
PCT/JP2013/001203
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English (en)
French (fr)
Japanese (ja)
Inventor
信樹 白垣
智和 杉谷
広行 及川
米谷　悟
金井　洋
信之 下田
一郎 大浦
菊池　仁志
Original Assignee
日鉄住金鋼板株式会社
新日鐵住金株式会社
日本パーカライジング株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 日鉄住金鋼板株式会社, 新日鐵住金株式会社, 日本パーカライジング株式会社 filed Critical 日鉄住金鋼板株式会社
Priority to MX2014010216A priority Critical patent/MX344444B/es
Priority to EP13755785.6A priority patent/EP2821223B1/en
Priority to JP2013530486A priority patent/JP5514369B2/ja
Priority to AU2013227872A priority patent/AU2013227872B2/en
Priority to KR1020147026987A priority patent/KR101508570B1/ko
Priority to CN201380011550.7A priority patent/CN104144782B/zh
Priority to ES13755785.6T priority patent/ES2652258T3/es
Priority to US14/381,203 priority patent/US9133346B2/en
Publication of WO2013128928A1 publication Critical patent/WO2013128928A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • Y10T428/1275—Next to Group VIII or IB metal-base component
    • Y10T428/12757—Fe
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
    • Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]

Definitions

  • the present invention relates to a surface-coated aluminum-containing zinc-based plated steel sheet having corrosion resistance, chemical resistance, blackening resistance, and formability, and a method for producing the same.
  • plating has been performed for a long time.
  • a typical composition of the plated layer in such a plated steel sheet for example, an alloy containing 1 to 75 mass% of aluminum, most of the zinc is zinc, and further contains a trace amount of a third component such as Si, Mg, and Ce—La. It is done.
  • the corrosion resistance of the conventional plated steel sheet is excellent, it means that it takes a long time to generate red rust due to the corrosion of the base iron. White rust and blackening occur, and the beautiful appearance of the plated steel sheet is impaired.
  • the surface of the plated layer tends to discolor over time due to the influence of acid rain.
  • Patent Document 1 molten Zn—Al alloy plating layer containing Al: 1.0 to 10%, Mg: 0.2 to 1.0%, Ni: 0.005 to 0.1% is disclosed.
  • a surface-treated plated steel sheet is mentioned.
  • the corrosion resistance, blackening resistance, paint adhesion, and plating appearance are excellent.
  • the present invention has been made in view of the above-mentioned reasons, and its object is to provide a surface-coated aluminum-containing zinc-based plated steel sheet that is excellent in corrosion resistance, acid resistance, and blackening resistance, and that does not contain chromium, and a method for producing the same. It is to provide.
  • the surface-coated aluminum-containing zinc-based plated steel sheet according to the first aspect of the present invention contains a water-dispersible resin (A), a cobalt compound (B), and water, and is in the range of pH 7.5 to 10
  • a surface treatment agent is applied to a plated steel sheet and dried to form a composite film containing the water-dispersible resin (A) and the cobalt compound (B), and the water-dispersible resin in the composite film
  • the composition ratio of (A) is 90% or more by mass ratio, and the dry film mass of the composite film per one side of the plated steel sheet is in the range of 0.5 to 3.5 g / m 2.
  • the dry film mass of the composite film per one side of the plated steel sheet is in the range of 0.5 to 3.5 g / m 2 ” means that the first surface and the second surface on the opposite side are the second surface. This means that the dry film mass of the composite film on at least the first surface of the plated steel sheet having a surface is in the range of 0.5 to 3.5 g / m 2 . That is, the dry film mass of the composite film on the first surface, or the dry film mass of the composite film on each of the first surface and the second surface is 0.5 to 3.5 g / it is within the range of m 2.
  • the corrosion resistance, blackening resistance, acid resistance, and molding processability of the surface-coated aluminum-containing zinc-based plated steel sheet are all improved, and chromium is not required to be contained in the composite film.
  • the environmentally and industrially useful value of the plated steel sheet is extremely high.
  • the mass ratio of cobalt atoms constituting the cobalt compound (B) to the water-dispersible resin (A) is 1/100 to 1/10000.
  • the blackening resistance and forming processability of the surface-coated aluminum-containing zinc-based plated steel sheet are further improved.
  • the cobalt compound (B) is cobalt sulfate, cobalt hydrochloride, and cobalt nitrate. At least one cobalt salt selected from
  • the blackening resistance of the surface-coated aluminum-containing zinc-based plated steel sheet is further improved.
  • the water-dispersible resin (A) is derived from a polyester polyol in the molecule.
  • Polyester polyurethane resin (aI) having a structural unit, polymerized units derived from (meth) acrylic acid ester having an alicyclic structure or glycidyl group, polymerized units derived from ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, and fat
  • Acrylic resin (aII) comprising a polymer having polymer units derived from (meth) acrylic acid ester having no ring structure and glycidyl group Among them, at least one is contained.
  • the surface-coated aluminum-containing zinc-based plated steel sheet according to the fifth aspect of the present invention contains the basic zirconium compound (C), the cobalt compound (D), and water in any one of the first to fourth aspects. Then, an undercoat containing the basic zirconium compound (C) and the cobalt compound (D) is formed by applying an aqueous surface conditioner having a pH in the range of 7.5 to 10 to the plated steel sheet. The composite coating is formed on the base coating, and the dry coating amount of the base coating per side of the plated steel plate is in the range of 0.05 to 0.8 g / m 2.
  • the Zr mass equivalent adhesion amount of the undercoat per one side of the steel sheet is in the range of 5 to 400 mg / m 2
  • the Co mass equivalent adhesion amount of the undercoat per one side of the plated steel sheet is 1 to 20 mg / m It is within the range of m 2.
  • the Zr mass conversion adhesion amount is the adhesion amount of Zr atoms contained in the undercoat
  • the Co mass conversion adhesion amount is the adhesion amount of Co atoms contained in the undercoat.
  • the blackening resistance and corrosion resistance of the surface-coated aluminum-containing zinc-based plated steel sheet are further improved.
  • the plated steel sheet contains zinc and aluminum, or zinc and A plating layer containing aluminum and magnesium, wherein the aluminum content in the plating layer is in the range of 1 to 75% by mass, and the magnesium content in the plating layer exceeds 0% by mass to 6.0% by mass Within the following range.
  • the plating layer contains Ni and 0% by mass within a range of more than 0% by mass and 1% by mass or less. 1 or more types are contained among Cr within the range of 1 mass% or less exceeding. In addition, these ratios are ratios with respect to the whole plating layer.
  • the plating layer contains Ca in a range of more than 0% and 0.5% by mass or less. Sr in the range of more than 0% to 0.5% by mass, Y in the range of more than 0% to 0.5% by mass, La in the range of more than 0% to 0.5% by mass or less And 1 or more types are contained among Ce in the range of 0.5 mass% or less exceeding 0%. In addition, these ratios are ratios with respect to the whole plating layer.
  • the plating layer contains 0 Si relative to Al in the plating layer. Within the range of 1 to 10% by mass.
  • the method for producing a surface-coated aluminum-containing zinc-based plated steel sheet comprises a water-dispersible resin (A), a cobalt compound (B), and water, and has a pH in the range of 7.5 to 10.
  • Prepared an aqueous surface treatment agent and a plated steel sheet The aqueous surface treatment agent is applied to the plated steel sheet and dried to contain the water-dispersible resin (A) and the cobalt compound (B), and the constituent ratio of the water-dispersible resin (A) is mass.
  • a composite film having a ratio of 90% or more is formed such that the dry film mass of the composite film per one side of the plated steel sheet is in the range of 0.5 to 3.5 g / m 2. To do.
  • the method for producing a surface-coated aluminum-containing zinc-based plated steel sheet according to an eleventh aspect of the present invention in the tenth aspect, contains a basic zirconium compound (C), a cobalt compound (D), and water, and has a pH of 7.
  • a basic zirconium compound (C) a cobalt compound (D)
  • water a basic zirconium compound
  • D cobalt compound
  • the undercoat containing the basic zirconium compound (C) and the cobalt compound (D) is applied to the plated steel sheet by applying the aqueous surface conditioner to the plated steel sheet, and the undercoat per one side of the plated steel sheet.
  • the amount of the dried film is in the range of 0.05 to 0.8 g / m 2
  • the Zr mass conversion adhesion amount of the base film per one side of the plated steel sheet is in the range of 5 to 400 mg / m 2
  • the undercoating film is formed such that the coating weight in terms of Co mass per one side of the plated steel sheet is in the range of 1 to 20 mg / m 2
  • the composite film is formed on the undercoating film.
  • a surface-coated aluminum-containing zinc-based plated steel sheet having excellent corrosion resistance, chemical resistance, blackening resistance, and formability can be obtained by performing a treatment without using chromium.
  • a surface-coated aluminum-containing zinc-based plated steel sheet (hereinafter referred to as a coated steel sheet) according to this embodiment includes a plated steel sheet and a composite coating laminated on the plated steel sheet.
  • the composite coating may be in direct contact with the plated steel plate, or another layer may be interposed between the plated steel plate and the composite coating. As an example of another layer, there is an undercoat described later.
  • the plated steel sheet includes a steel sheet and a plating layer formed on the steel sheet.
  • the plating layer is formed by a hot dipping process or the like.
  • the plating layer preferably contains zinc and aluminum as constituent elements, or further contains magnesium.
  • the surface of the plating layer is covered with a thin oxide film formed in the aluminum phase in the plating layer, and this oxide film exhibits a protective action, so that the corrosion resistance of the surface of the plating layer in particular is improved.
  • zinc suppresses edge creep particularly at the cut end face of the coated plated steel sheet due to sacrificial anticorrosive action. For this reason, especially high corrosion resistance is provided to a covering plating steel plate.
  • the plating layer further contains magnesium, which is a base metal rather than zinc, both the protective action due to aluminum of the plating layer and the sacrificial anticorrosive action due to zinc are strengthened, and the corrosion resistance of the coated plated steel sheet is further increased. improves.
  • the content of aluminum in the plating layer is not particularly limited, but is preferably in the range of 1 to 75% by mass, and more preferably 5 to 65% by mass. In particular, this proportion is preferably in the range of 5 to 15% by mass.
  • this ratio is 5 to 15% by mass, the protective effect due to aluminum works mainly in the sacrificial anticorrosive effect due to zinc in the plating layer, so that the corrosion resistance of the coated plated steel sheet is particularly improved. It is also preferable that this ratio is in the range of 45 to 65% by mass. In this case, the corrosion resistance of the coated plated steel sheet is particularly improved by the sacrificial anticorrosive effect due to zinc acting mainly on the protective effect due to aluminum in the plating layer.
  • the content ratio of magnesium in the plating layer is not particularly limited, but is preferably in the range of more than 0% by mass to 6.0% by mass, particularly in the range of 0.1 to 5.0% by mass. Preferably there is.
  • the plating layer may further contain one or more elements selected from Si, Ni, Ce, Cr, Fe, Ca, Sr, rare earth, and the like as constituent elements.
  • the plating layer contains one or more elements selected from Ni, Cr, and Y; alkaline earth elements such as Ca and Sr; and rare earth elements such as La and Ce, the protective action caused by aluminum in the plating layer And the sacrificial anticorrosive action due to zinc are strengthened together, the corrosion resistance of the coated plated steel sheet is further improved.
  • the plating layer preferably contains one or more of Ni and Cr.
  • Ni it is preferable that the ratio of Ni in a plating layer is in the range of more than 0 mass% and 1 mass% or less. More preferably, this ratio is in the range of 0.01 to 0.5 mass%.
  • Cr it is preferable that the ratio of Cr in a plating layer is in the range of more than 0 mass% and 1 mass% or less. More preferably, this ratio is in the range of 0.01 to 0.5 mass%. In these cases, the corrosion resistance of the coated plated steel sheet is particularly improved.
  • the plating layer contains one or more of Ca, Sr, Y, La and Ce.
  • the proportion of Ca in the plating layer is preferably in the range of more than 0% and 0.5% by mass or less. More preferably, this ratio is in the range of 0.001 to 0.1% by mass.
  • the ratio of Sr in the plating layer is preferably in the range of more than 0% and 0.5% by mass or less. More preferably, this ratio is in the range of 0.001 to 0.1% by mass.
  • the proportion of Y in the plating layer is preferably in the range of more than 0% and 0.5% by mass or less.
  • this ratio is in the range of 0.001 to 0.1% by mass.
  • a plating layer contains La
  • the ratio of La in a plating layer is in the range of 0.5 mass% or less exceeding 0%. More preferably, this ratio is in the range of 0.001 to 0.1% by mass.
  • the plating layer contains Ce
  • the proportion of Ce in the plating layer is preferably in the range of more than 0% and 0.5% by mass or less. More preferably, this ratio is in the range of 0.001 to 0.1% by mass. In these cases, the corrosion resistance of the coated plated steel sheet is particularly improved, and the effect of suppressing defects on the surface of the plated layer is expected.
  • the mechanical workability of the coated plated steel sheet is improved. This is because Si suppresses the growth of the alloy layer at the interface between the plating layer and the steel sheet, thereby maintaining proper adhesion between the plating layer and the steel sheet and improving workability. Furthermore, it is expected that the corrosion resistance of the coated plated steel sheet is further improved by forming an alloy with magnesium.
  • the ratio of Si to Al in the plating layer is preferably in the range of 0.1 to 10% by mass. In this case, the mechanical workability of the coated plated steel sheet and the corrosion resistance of the machined portion are further improved.
  • the Si content is more preferably in the range of 1 to 5% by mass.
  • the plating layer may contain elements inevitably mixed other than those described above.
  • the composite film contains a water-dispersible resin (A) and a cobalt compound (B).
  • This composite film is formed by applying an aqueous surface treatment agent to a plated steel sheet and drying it.
  • This metal-based surface treatment agent contains a water-dispersible resin (A), a cobalt compound (B), and water, and has a pH in the range of 7.5 to 10.
  • the water dispersible resin (A) will be described in more detail.
  • the presence form of the resin in water is roughly classified into two types, water-soluble and water-dispersible. Among them, in this embodiment, a water dispersible resin is used.
  • a water-dispersible resin is a resin that forms an emulsion or a dispersion by being dispersed in a particulate form in water.
  • the water-dispersible resin (A) in this embodiment is dispersed in the form of particles in an aqueous surface treatment agent to form an emulsion or a dispersion.
  • the water-dispersible resin (A) is stably present in a dispersed state in the aqueous surface treatment agent. This is considered to be because the particles of the water-dispersible resin (A) are ion-dispersed due to the orientation of carboxyl groups on the surface of the particles of the water-dispersible resin (A), and thus are anionic and ion-dispersed. .
  • the water dispersible resin (A) preferably contains at least one of the following polyester polyurethane resin (aI) and acrylic resin (aII).
  • Polyester polyurethane resin (aI) having a structural unit derived from polyester polyol in the molecule.
  • An acrylic resin (aII) comprising a polymer comprising polymerized units derived from an acrylate ester.
  • the polyester polyurethane resin (aI) will be described.
  • Examples of the raw material for the polyester polyurethane resin (aI) include diisocyanate or polyisocyanate having two or more isocyanate groups, diol or polyol, diamine or polyamine, and an acid component.
  • the polyester polyurethane resin (aI) is obtained by a general synthesis method, and the synthesis method is not particularly limited. In the production of the polyester polyurethane resin (aI), a polyester polyol is first produced, and then the polyester polyurethane resin (aI) is produced from a raw material containing the polyester polyol.
  • the polyester polyurethane resin (aI) In order to make the polyester polyurethane resin (aI) aqueous, it is preferable to copolymerize dimethylol alkyl acid when the polyester polyol and hydrogenated isocyanate are polymerized. In this case, the polyester polyurethane resin (aI) becomes aqueous (water-dispersed) by self-emulsification.
  • the polyester polyurethane resin (aI) is made water-based by such a technique, since the emulsifier is not used at the time of making water-based, excellent water resistance is imparted to the composite film, and thus the corrosion resistance and acid resistance of the coated plated steel sheet are improved. It leads to.
  • an emulsifier may be used as long as the storage stability of the aqueous surface treatment agent is maintained and the other performance is not deteriorated.
  • polyester polyol examples include polyesters obtained by a dehydration condensation reaction between a glycol component and an acid component such as a polyvalent carboxylic acid, a hydroxycarboxylic acid, or an ester-forming derivative thereof.
  • the polyester polyol may be a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone.
  • the polyester polyol may be a copolymer of these polyesters.
  • glycol component examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane.
  • Examples thereof include diol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone, and alkylene oxide adducts thereof.
  • Examples of the acid component include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, Isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p
  • Examples include '-dicarboxylic acids, anhydrides of these dicarboxylic acids, ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, and p- (2-hydroxyethoxy) benzoic acid.
  • Isocyanates include aliphatic, alicyclic or aromatic polyisocyanates.
  • Specific examples of the isocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 2,4′-dicyclohexylmethane diisocyanate.
  • Isophorone diisocyanate 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene Isocyanates, and include tetramethylxylylene diisocyanate.
  • tetramethylene diisocyanate hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate
  • aliphatic or alicyclic polyisocyanate compounds such as In this case, not only acid resistance and corrosion resistance of the composite film, but also blackening resistance (including yellowing) is improved.
  • the polyester polyurethane resin (aI) may be mixed with an organic solvent in order to improve the stability during resin synthesis and the film-forming property during low-temperature drying.
  • organic solvent include N-methyl-2-pyrrolidone, diethylene glycol monobutyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and the like.
  • acrylic resin (aII) improves the slip resistance and weather resistance of the coated plated steel sheet.
  • Acrylic resin (aII) is made from (meth) acrylic acid ester having an alicyclic structure or glycidyl group, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, and (meth) acrylic acid ester having no alicyclic structure and glycidyl group Is synthesized.
  • (meth) acrylic acid esters having an alicyclic structure or a glycidyl group include bornyl acrylate, isobornyl acrylate, bornyl methacrylate, isobornyl methacrylate, ( Examples include 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclodecyl (meth) acrylate, and cyclododecyl (meth) acrylate.
  • Examples of the (meth) acrylic acid ester having a glycidyl group include glycidyl (meth) acrylate.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like.
  • (Meth) acrylic acid ester without alicyclic structure and glycidyl group includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid Butyl, isobutyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate, decyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, acrylonitrile and the like.
  • the method for synthesizing the acrylic resin (aII) is not particularly limited, and examples thereof include a radical polymerization method using an emulsifier and a peroxide.
  • the emulsifier include anionic active agents such as polyoxyethylene alkyl sodium salt and sodium alkylbenzene sulfonate, nonionic active agents such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester and sorbitan alkyl ester, and hydrophobic groups.
  • One or more selected from reactive emulsifiers having a functional group capable of radical polymerization are used.
  • the acrylic resin (aII) may be silane-modified using a silane coupling agent.
  • the type of silane coupling agent and the amount of modification are not particularly limited.
  • Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltris (2-methoxyethoxysilane), vinyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloyloxypropyl) trimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N- (2-aminoethyl) 3- Aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-amin
  • the coated plated steel sheet exhibits excellent blackening resistance.
  • the water-dispersible resin (A) preferably contains both the polyester polyurethane resin (aI) and the acrylic resin (aII) in order to further improve the blackening resistance of the coated plated steel sheet in a severe environment. .
  • the ratio of the polyester polyurethane resin (aI) and the acrylic resin (aII) in the water-dispersible resin (A) is not particularly limited, but the ratio of the mass of the polyester polyurethane resin (aI) to the mass of the acrylic resin (aII) (mass Ratio) is preferably in the range of 69/31 to 40/60, more preferably in the range of 60/40 to 45/55, and even more preferably in the range of 55/45 to 50/50. When this mass ratio is 69/31 or less, good acid resistance of the composite coating is maintained. When this mass ratio is 40/60 or more, good corrosion resistance, acid resistance, and moldability of the composite coating are maintained.
  • the water-dispersed resin (A) may be mixed with an emulsifier for improving the water-dispersibility of the water-dispersed resin (A) as long as the effects of the present invention are not impaired.
  • cobalt compound (B) Details of the cobalt compound (B) will be described. Specific examples of the cobalt compound (B) include cobalt nitrate (II), cobalt sulfate (II), cobalt acetate (II), cobalt oxalate (II), cobalt nitrate (II), cobalt acetate (II), and oxalic acid. Examples include cobalt (III), cobalt (IV) chloride, cobalt (III) oxide, and cobalt (IV) oxide. The cobalt compound (B) preferably contains at least one cobalt salt selected from cobalt sulfate, cobalt hydrochloride, and cobalt nitrate.
  • the cobalt compound (B) preferably contains at least one of cobalt nitrate (II), cobalt sulfate (II), and cobalt chloride (II). Furthermore, it is even more preferable that the cobalt compound (B) contains cobalt (II) nitrate.
  • the composition ratio of the water-dispersible resin (A) in the composite film is 90% or more in terms of mass ratio, thereby giving the composite film good corrosion resistance, acid resistance, and molding processability, and an aqueous surface treatment. Good storage stability is imparted to the agent.
  • the constituent ratio of the water dispersible resin (A) is more preferably 95% or more, and even more preferably 98% or more.
  • the composite film necessarily contains the cobalt compound (B), but from the viewpoint of economy, it is preferable that the amount of the cobalt compound (B) is as small as possible.
  • the cobalt compound (B) When the cobalt compound (B) is used in this way, the cobalt compound (B) is uniformly dispersed in the composite film formed from the aqueous surface treatment agent. Part of this cobalt compound (B) modifies the surface of the plating layer by reaction with the surface of the plating layer, thereby improving the blackening resistance of the coated plated steel sheet. Another part of the cobalt compound (B) dispersed in the composite film diffuses into the composite film under a high-temperature and high-humidity atmosphere, thereby suppressing the phenomenon that the surface of the plating layer is discolored. Thereby, practically, the blackening resistance of the coated plated steel sheet is maintained for a long time.
  • the cobalt compound (B) exerts an action of protecting the surface of the plating layer and suppressing the discoloration.
  • the presence of the cobalt compound (B) between the mold and the plating layer makes it difficult to cause damage such as galling to the plating layer.
  • the surface layer becomes difficult to discolor black.
  • the ratio of the cobalt compound (B) to the water-dispersible resin (A) is not particularly limited, but the mass ratio of cobalt atoms constituting the cobalt compound (B) to the water-dispersible resin (A) is 1/100 to It is preferable to be within the range of 1/10000. This ratio is more preferably in the range of 1/500 to 1/5000. When this ratio is 1/100 or less, good storage stability of the aqueous surface treatment agent is maintained. When this ratio becomes larger than 1/100, the performance improvement due to the use of the cobalt compound (B) is saturated, which is economically undesirable. When this ratio is 1 / 10,000 or more, blackening resistance, acid resistance, and resistance to deformation during molding are particularly improved, and excellent effects are exhibited even when the plated steel sheet has a plating layer with a high aluminum content. Is done.
  • the aqueous surface treatment agent may further contain a plasticizer.
  • the plasticizer include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, and benzyl alcohol.
  • the content of the plasticizer in the aqueous surface treatment agent is preferably in the range of 15 to 30% by mass, and in the range of 20 to 25% by mass with respect to the solid content mass of the water-dispersible resin (A). More preferably. When the content is 15% by mass or more, the effect of adding a plasticizer is sufficiently exhibited. As a result, good film-forming properties are imparted to the aqueous surface treatment agent, and the composite coating has good corrosion resistance and acid resistance. Maintained. When this content is 30% by mass or less, good storage stability of the aqueous surface treatment agent is maintained.
  • the aqueous surface treatment agent pH is in the range of 7.5 to 10. If the pH is less than 7.5, the storage stability of the aqueous surface treatment agent tends to decrease. If the pH exceeds 10, the passive layer on the plated steel sheet surface is destroyed, and the performance of the plated layer itself Will drop significantly.
  • An aqueous surface treatment agent is applied onto the surface of the plated steel sheet, and the aqueous surface treatment agent is further dried to form a composite film.
  • Examples of the application method of the aqueous surface treatment agent include a roll coating method, a spray method, a dipping method, a shower ringer method, and an air knife method.
  • the method for drying the aqueous surface treatment agent may be natural drying or forced drying using a heating apparatus such as an electric furnace, a hot air furnace, an induction heating furnace or the like.
  • the ultimate temperature of the plated steel sheet when the aqueous surface treatment agent is dried is preferably in the range of 60 to 180 ° C, more preferably in the range of 80 to 150 ° C, and in the range of 100 to 150 ° C. If it is in, it is more preferable.
  • the dry film mass of the composite film on the plated steel sheet is in the range of 0.5 to 3.5 g / m 2 .
  • This dry film mass is the dry film mass per one side of the plated steel sheet. That is, the dry film mass of the composite film on at least the first surface of the plated steel sheet having the first surface and the second surface opposite to the first surface is in the range of 0.5 to 3.5 g / m 2 . It is. That is, the dry film mass of the composite film on the first surface, or the dry film mass of the composite film on each of the first surface and the second surface is in the range of 0.5 to 3.5 g / m 2 . It is.
  • the dry film mass is less than 0.5 g / m 2 , the effect of forming the composite film cannot be sufficiently obtained, and excellent corrosion resistance, acid resistance, and moldability cannot be imparted to the coated plated steel sheet. If the dry film mass is greater than 3.5 g / m 2 , a long drying time is required to prevent film formation defects. If the dry film mass is greater than 3.5 g / m 2 , the performance improvement will be saturated, resulting in productivity and economic loss.
  • the plated steel sheet Before the composite coating is formed on the plated steel sheet, the plated steel sheet may be washed in advance to remove oil and contaminants adhering to the surface of the plated steel sheet and clean the surface of the plated layer.
  • the cleaning agent used for cleaning include well-known cleaning agents in which inorganic components such as acidic components and alkaline components, chelating agents, surfactants and the like are blended.
  • the pH of the cleaning agent may be either alkaline or acidic as long as the performance of the coated plated steel sheet is not impaired.
  • Co may be precipitated on the plated steel sheet by bringing the aqueous surface conditioner containing a cobalt compound and adjusted to an acidic pH into contact with the surface of the plated steel sheet. .
  • the pH of the aqueous surface conditioner may be adjusted to be alkaline.
  • a treatment method using an aqueous surface conditioner either immersion or spray treatment can be applied.
  • the amount of Co deposited on the plated steel sheet is preferably in the range of 0.5 to 15 mg / m 2 . That is, it is preferable that the coating amount in terms of Co mass per one side of the plated steel sheet of the base film formed from the aqueous surface conditioner is in the range of 0.5 to 15 mg / m 2 .
  • cobalt compound (B) contained in a composite film can be used suitably.
  • known acid components such as sulfuric acid, hydrochloric acid and nitric acid, and known base components such as ammonia and sodium hydroxide can be used. Since the pH of the aqueous metal surface treatment agent used for forming the composite film laminated on the base film is close to the alkali (pH 7.5 to 10), the pH of the aqueous surface conditioner is also more alkaline than the acidic range. From the viewpoint of an industrial process, it is preferable.
  • the pH of the aqueous surface conditioner is more preferably in the range of 7.5 to 10 which is the same as the aqueous metal surface treatment agent for the composite film.
  • a base film is formed on the plated steel sheet from a basic zirconium compound (C), a cobalt compound (D), and an alkaline aqueous surface conditioner containing water.
  • a composite film may be formed.
  • the undercoat contains a basic zirconium compound (C) and a cobalt compound (D).
  • the blackening resistance of the coated plated steel sheet is maintained for a longer period.
  • the base film contains the basic zirconium compound (C) in addition to the cobalt compound (D), not only the blackening resistance but also the corrosion resistance of the coated plated steel sheet can be maintained for a long time. The reason is considered as follows.
  • the undercoat contains the basic zirconium compound (C)
  • the undercoat becomes dense, and thus the corrosion resistance of the coated plated steel sheet is improved.
  • the aqueous surface conditioner contacts and reacts with the surface of the plating layer, whereby the cobalt compound (D) is plated with the base coating in the matrix composed of the basic zirconium compound (C) in the base coating. Presumably present (segregation) at a high concentration near the interface with the layer. Therefore, even under an environmental atmosphere where blackening is likely to occur originally, the cobalt compound (D) is not consumed at once, and the blackening resistance of the coated plated steel sheet is continuously exhibited over a long period of time. it is conceivable that.
  • the aqueous surface conditioner is alkaline as is the case with the aqueous surface treatment agent used to form the composite film.
  • the plating layer contains magnesium, this magnesium is easily dissolved in an acidic solution.
  • the aqueous surface conditioner is alkaline, magnesium in the plating layer is difficult to dissolve in the aqueous surface treatment agent. For this reason, it becomes difficult to damage a plating layer, the characteristic of a plating layer is fully exhibited, and also the characteristic of this plating layer and the characteristic of a base film can express synergistically.
  • the pH of the aqueous surface conditioner is in the range of 7.5 to 10 like the pH of the aqueous surface treatment agent. This is particularly advantageous in terms of process. Furthermore, when the pH of the aqueous surface conditioner is in the range of 7.5 to 10, the storage stability of the aqueous surface conditioner and the liquid stability during processing are improved.
  • known acid components such as sulfuric acid, hydrochloric acid and nitric acid, and known base components such as ammonia, amines and sodium hydroxide can be used.
  • the basic zirconium compound (C) is a kind selected from, for example, basic zirconium, basic zirconyl, basic zirconyl salt, basic zirconium carbonate, basic zirconyl carbonate, basic zirconium carbonate salt, and basic zirconyl carbonate salt
  • the above compounds can be contained.
  • the salt include ammonium salt, sodium, potassium, lithium alkali metal salt, amine salt and the like.
  • the basic zirconium compound (C) comprises zirconyl ammonium carbonate [(NH 4 ) 2 ZrO (CO 3 ) 2 ], potassium zirconyl carbonate [K 2 ZrO (CO 3 ) 2 ], zirconyl sodium carbonate [ Na 2 Zr (CO 3 ) 2 ], zirconium carbonate ⁇ (NH 4 ) 2 [Zr (CO 3 ) 2 (OH) 2 ⁇ , potassium zirconium carbonate ⁇ K 2 [Zr (CO 3 ) 2 (OH) 2 ⁇ And one or more selected from zirconium carbonate sodium ⁇ Na 2 [Zr (CO 3 ) 2 (OH) 2 ⁇ .
  • the basic zirconium compound (C) is composed of zirconyl ammonium carbonate [(NH 4 ) 2 ZrO (CO 3 ) 2 ] and ammonium zirconium carbonate ⁇ (NH 4 ) 2 [Zr (CO 3 ) 2 (OH) 2 ⁇ . It is preferable to contain at least one.
  • cobalt compound (D) Details of the cobalt compound (D) will be described. Specific examples of the cobalt compound (D) include cobalt nitrate (II), cobalt sulfate (II), cobalt acetate (II), cobalt oxalate (II), cobalt nitrate (II), cobalt acetate (II), and oxalic acid. Examples include cobalt (III), cobalt (IV) chloride, cobalt (III) oxide, and cobalt (IV) oxide. The cobalt compound (D) can contain one or more selected from these compounds.
  • the cobalt compound (D) preferably contains at least one cobalt salt selected from cobalt sulfate, cobalt hydrochloride, and cobalt nitrate. That is, the cobalt compound (B) preferably contains at least one of cobalt nitrate (II), cobalt sulfate (II), and cobalt chloride (II). It is even more preferable that the cobalt compound (D) contains cobalt (II) nitrate.
  • a basic zirconium compound (C), a cobalt compound (D), and water are mixed, and if necessary, at least one of an acid component and a base component for pH adjustment is blended, so that an aqueous surface conditioning agent is added. Is prepared.
  • the amount of the basic zirconium compound (C) and the cobalt compound (D) in the aqueous surface conditioner is appropriately adjusted according to the applicability of the aqueous surface conditioner, the zirconium content and the cobalt content desired for the undercoat. Is done.
  • An undercoat is formed by applying an aqueous surface conditioner to the plating layer.
  • an aqueous surface conditioner to the plating layer.
  • the base film is formed by washing with water after the aqueous surface conditioner contacts the plating layer by dipping, spraying, or the like.
  • the temperature of the aqueous surface conditioner applied to the plating layer is preferably within the range of 10 to 80 ° C.
  • the aqueous surface conditioner should be washed with water after the aqueous surface conditioner contacts the plating layer by roll coating, spraying, dipping, shower ringer method, air knife method, curtain flow method, etc.
  • the undercoat is formed by drying completely.
  • the temperature of the aqueous surface conditioner applied to the plating layer is preferably in the range of 10 to 150 ° C., more preferably in the range of 30 to 100 ° C.
  • the dry film amount of the base film per side of the plated steel sheet is preferably in the range of 0.05 to 0.8 g / m 2 .
  • the amount of the dry film is 0.05 g / m 2 or more, the blackening resistance and corrosion resistance improving action by the base film is remarkably exhibited.
  • the amount of the dry film is 0.8 g / m 2 or less, the base film is particularly densified, so that the effect of improving blackening resistance and corrosion resistance is remarkably exhibited.
  • the Zr mass conversion adhesion amount of the undercoat per one side of the plated steel sheet is in the range of 5 to 400 mg / m 2 . In this case, the effect of improving blackening resistance and corrosion resistance is remarkably exhibited.
  • the Co mass equivalent adhesion amount of the undercoat per one side of the plated steel sheet is preferably in the range of 1 to 20 mg / m 2 . In this case, the effect of improving blackening resistance and corrosion resistance is remarkably exhibited.
  • Aqueous surface treatment agent (3-1) Water dispersible resin (A)
  • the urethane resin (aI) and acrylic resin (aII) shown in Table 2 were obtained by the synthesis method shown below.
  • (Urethane resin (aI1)) 100 parts by mass of a polyester polyol having a number average molecular weight of 2000 synthesized from 1,6-hexanediol, neopentyl glycol and adipic acid, 5 parts by mass of 2,2-dimethyl-1,3-propanediol, and 2,2-dimethylol
  • propionic acid 100 parts by mass of 2,4-dicyclohexylmethane diisocyanate and 100 parts by mass of N-methyl-2-pyrrolidone into the reaction vessel and reacting them, a free isocyanate group with respect to the nonvolatile content
  • a urethane prepolymer having a content of 5% by mass was obtained.
  • composition Blended in composition (mass%) and reacted for several hours at 80 to 85 ° C. using ammonium persulfate as a polymerization catalyst, then pH adjustment and concentration adjustment with ammonia water and deionized water, solid content concentration 40% Water dispersible acrylic To obtain the fat.
  • aqueous surface treating agent (Examples 1-41 and Comparative Examples 1-5) Surface treatment with a solid content concentration of 30% by blending water-dispersible resin (A), cobalt compound (B), and deionized water, and adjusting the pH by adding ammonia or ammonium nitrate as required. An agent (aqueous surface treatment agent) was obtained.
  • Tables 6 and 7 below show the types of the water-dispersible resin (A) and the cobalt compound (B) used in each example and comparative example, the blending ratio thereof, and the pH of the aqueous surface treatment agent.
  • “(aI) / (aII)” represents the mass ratio of the acrylic resin (aI) to the urethane resin (aII), and “Co / (a) mass ratio” represents the water dispersion.
  • the mass ratio of the cobalt atoms constituting the cobalt compound (B) to the water-soluble resin (A) is shown, and “(A) / ((A) + (B)) (mass%)” represents the water-dispersible resin (A ) And the cobalt compound (B), the mass percentage of the water-dispersible resin (A) with respect to the total amount is shown.
  • aqueous surface treating agent (Comparative Example 5) 25 parts by mass of a titanium-containing aqueous liquid prepared by the method shown below, 54.6 parts by mass of a water-dispersible acrylic resin prepared by the method shown below, 0.4 parts by mass of cobalt nitrate, and 20 parts by mass of ammonium zircon fluoride An aqueous surface treating agent was obtained by blending.
  • Tianium-containing aqueous solution A mixture of 10 parts by mass of tetraiso-propoxytitanium and 10 parts by mass of iso-propanol was dropped into a mixture of 30 parts by mass of hydrogen peroxide 10 parts by mass and deionized water 100 parts by mass at 20 ° C. over 1 hour. did. Thereafter, aging was carried out at 25 ° C. for 2 hours to obtain a yellow transparent slightly viscous titanium-containing aqueous liquid.
  • the reducing agent aqueous solution was 5% by mass (4. oxidizer aqueous solution obtained by dissolving 5 parts by mass of perbutyl H (t-butylhydroxyperoxide, active ingredient 69% by mass) in 83.5 parts by mass of deionized water. 43 parts by mass) and 2.5 parts by mass of sodium formaldehyde sulfoxylate were dissolved in 83.5 parts by mass of deionized water.
  • the mixture was further heated to 60 ° C. and then kept at this temperature.
  • the remaining pre-emulsion was added dropwise over 1.5 hours, the remaining oxidizing agent aqueous solution for 3.5 hours, and the remaining reducing agent aqueous solution over 3.5 hours. While the dropping of the oxidizing agent aqueous solution and the reducing agent aqueous solution is continued, after one hour has elapsed since the dropping of the first-stage pre-emulsion was completed, the monomer mixture No. 1 having the following composition was used. 2 (second stage) was added dropwise over 1 hour.
  • the liquid mixture is maintained at a temperature of 60 ° C. for 1 hour, and then the temperature of the liquid mixture is lowered to 40 ° C. or lower.
  • An antiseptic Naippon Enviro Chemicals Co., Ltd., product name Suraoff EX 0.35 parts by mass and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 83.5 parts by mass were added.
  • a water dispersible acrylic resin having a pH of 8.0 and a nonvolatile content (solid content) of 31% by mass was obtained.
  • composition of monomer mixture No. 1 Deionized water: 166.5 parts by mass. Aqualon RN-50: 6.6 parts by mass. Aqualon RN-2025: 53 parts by mass. Styrene: 35 parts by mass. Methyl methacrylate: 163.5 parts by mass. 2-ethylhexyl acrylate: 105 parts by mass. 2-hydroxyethyl methacrylate: 5 parts by mass. Methacrylic acid: 3 parts by mass. Acrylonitrile: 38.5 parts by mass. Tasha lead decanethiol: 1 part by mass.
  • composition of monomer mixture No. 2 Styrene 15 parts by mass.
  • Methyl methacrylate 84.5 parts by mass.
  • 2-ethylhexyl acrylate 22.5 parts by mass.
  • 2-hydroxyethyl methacrylate 4.25 parts by mass.
  • Methacrylic acid 6 parts by mass.
  • Acrylonitrile 15 parts by mass.
  • ⁇ -methacryloxypropyltrimethoxysilane 2.75 parts by mass.
  • Aqueous surface conditioner (4-2) Basic zirconium compound (C) As the basic zirconium compound (C), (c1) to (c3) shown in Table 8 below were used.
  • Cobalt compound (D) As the cobalt compound (D), (d1) to (d4) shown in Table 9 below were used.
  • aqueous surface conditioner (Examples 33 to 41) A basic zirconium compound (C), a cobalt compound (D), and deionized water were blended, and an aqueous surface conditioner was obtained by adjusting the pH by adding ammonia or ammonium nitrate as necessary. Table 10 below shows the types of the basic zirconium compound (C), the types of the cobalt compound (D), and the pH of the aqueous surface conditioner used for obtaining the aqueous surface conditioner.
  • an aqueous surface conditioner was applied to the plated steel sheet with a bar coater before the treatment using the above-described aqueous surface treatment agent. Subsequently, the plated steel sheet was dried by heating in a 200 ° C. atmosphere so as to reach the ultimate plate temperature (PMT) shown in Table 12. As a result, an undercoat film having a dry film mass shown in Table 12 was formed. Thereafter, a composite film was formed on the base film using an aqueous surface treatment agent under the above conditions.
  • PMT ultimate plate temperature
  • Color measurement based on the L * a * b * color system was performed for each of the coated steel sheet before treatment and the coated steel sheet after treatment.
  • the color tone measurement was performed using a spectrocolorimeter (model number SC-T45) manufactured by Suga Test Instruments Co., Ltd.
  • blackening resistance was evaluated as follows. In this test, if the evaluation is 3 to 5, it is judged that the coated steel sheet has excellent blackening resistance in practical use. 5; ⁇ E is less than 2. 4: ⁇ E is 2 or more and less than 5. 3: ⁇ E is 5 or more and less than 10. 2: ⁇ E is 10 or more and less than 15. 1: ⁇ E is 15 or more.
  • the coated plated steel sheet was excellent in corrosion resistance, acid resistance, blackening resistance and molding processability, and the storage stability of the aqueous surface treatment agent was also excellent. It was a thing.
  • both the base film and the composite film were formed on the coated plated steel sheet, and the corrosion resistance and blackening resistance of the coated plated steel sheet were further improved.
  • the use of the surface-coated aluminum-containing zinc-based plated steel sheet according to the present invention is not limited, but can be used in the fields of building material products, home appliances, automobile members, and the like. In particular, it is preferably applied to building material products that are used outdoors for a long time.

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PCT/JP2013/001203 2012-02-28 2013-02-28 表面被覆アルミニウム含有亜鉛系めっき鋼板及びその製造方法 WO2013128928A1 (ja)

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MX2014010216A MX344444B (es) 2012-02-28 2013-02-28 Lamina de acero depositada con aluminio y zinc recubierta en la superficie y metodo de preparacion de la misma.
EP13755785.6A EP2821223B1 (en) 2012-02-28 2013-02-28 Surface-coated aluminum and zinc plated steel sheet and method of preparing same
JP2013530486A JP5514369B2 (ja) 2012-02-28 2013-02-28 表面被覆アルミニウム含有亜鉛系めっき鋼板及びその製造方法
AU2013227872A AU2013227872B2 (en) 2012-02-28 2013-02-28 Surface-coated aluminum-containing galvanized steel sheet and method for producing same
KR1020147026987A KR101508570B1 (ko) 2012-02-28 2013-02-28 표면 피복 알루미늄 및 아연 도금 강판 및 그 제조 방법
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ES13755785.6T ES2652258T3 (es) 2012-02-28 2013-02-28 Chapa de acero aluminizado y cincado revestida superficialmente y procedimiento de preparación de la misma
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MX2018007963A (es) * 2016-03-09 2018-11-09 Nippon Steel & Sumitomo Metal Corp Lamina de acero con superficie tratada y metodo para producir la lamina de acero con superficie tratada.
CN109689916B (zh) * 2016-09-05 2023-08-01 杰富意钢铁株式会社 热浸镀Al-Zn系钢板
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US10053753B2 (en) 2013-02-28 2018-08-21 Nippon Steel & Sumikin Coated Sheet Corporation Aluminum-zinc plated steel sheet and method for producing the same
CN104109855A (zh) * 2014-06-19 2014-10-22 锐展(铜陵)科技有限公司 一种隔热铝合金表面处理剂
WO2016171281A1 (ja) * 2015-04-24 2016-10-27 日本パーカライジング株式会社 金属材料用表面処理剤及び金属材料
JP2017067483A (ja) * 2015-09-28 2017-04-06 新日鐵住金株式会社 耐候性鋼材の錆層評価方法

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EP2821223B1 (en) 2017-09-13
EP2821223A4 (en) 2015-08-12
MY153896A (en) 2015-04-08
JP5514369B2 (ja) 2014-06-04
US9133346B2 (en) 2015-09-15
KR20140124865A (ko) 2014-10-27
CN104144782B (zh) 2015-10-21
EP2821223A1 (en) 2015-01-07
JPWO2013128928A1 (ja) 2015-07-30
US20150044498A1 (en) 2015-02-12
MX2014010216A (es) 2015-06-02
ES2652258T3 (es) 2018-02-01
MX344444B (es) 2016-12-15
AU2013227872B2 (en) 2014-10-16
TW201348514A (zh) 2013-12-01
TWI482880B (zh) 2015-05-01
KR101508570B1 (ko) 2015-04-07

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